Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/34—Chemical or biological purification of waste gases
  • B01D53/46—Removing components of defined structure
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B35/00—Boron; Compounds thereof
  • C01B35/02—Boron; Borides
  • C01B35/023—Boron
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2251/00—Reactants
  • B01D2251/20—Reductants
  • B01D2251/202—Hydrogen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/10—Single element gases other than halogens
  • B01D2257/104—Oxygen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2259/00—Type of treatment
  • B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
  • B01D2259/818—Employing electrical discharges or the generation of a plasma

Definitions

• the present invention relates to a purification method for removing oxygen from materials.
• Oxygen contamination of material represents a problem for a wide range of raw materials in science and industry. Removal or depleting of oxygen contamination often represent a problem or a task which can be overcome only heavily and under big efforts. These problems often are amplified by the essential character of oxygen impurities which are caused by absorption and/or reaction of raw materials with naturally abandoned O 2 . Due to the presence of oxygen in air oxygen contaminations are practically all- pervasive. In addition to this, the removal of oxygen contaminations is often complicated by the formation of oxides of high stability.
• the task of the subject invention was to provide a purification method for removing oxygen, in particular a procedure allowing to avoid a thermal treatment or a treatment leaving a reducing agent within the material.
• this task was resolved by a purification method for removing oxygen from material wherein a material, containing oxygen impurities, is subjected to a treatment with hydrogen-based plasma.
• the procedure of the present invention consisting in the treatment with hydrogen-based plasma generally can be applied for all materials in order to remove impurities containing oxygen.
• a temperature stable material is used, in particular a material which distinctly does not evaporate at temperatures of ⁇ 600 0 C, more preferably of ⁇ 750 0 C, and most preferably of ⁇ 950 0 C and which is not subject to any other degradation process.
• the used materials are elements, in particular metals or non- metallic elements.
• compounds consisting of more than one element can be purified by the present invention.
• the purification method of the invention is used for removing oxygen from boron, in particular from amorphous boron.
• Oxygen contamination of amorphous boron is especially difficult to remove and represents a serious problem.
• Industrial routes for producing amorphous boron usually include reduction of B 2 O 3 by a suitable reducing agent. With such a treatment, an amorphous boron material is usually obtained in such a treatment which contains up to 4 mass-% of oxygen. This hinders the application of this material, e.g. for chemical preparations since in many fields of application it is necessary that the amorphous boron oxygen used is free or at least shows a minimally possible oxygen content.
• Amorphous boron is often used for this purpose since it shows a considerably higher chemical reactivity in chemical reactions compared to crystalline boron.
• attempts to purify amorphous boron by any kind of thermal treatment leading to boron oxide evaporation result in crystallization of boron and thus the transformation of the amorphous boron to the undesired crystalline form.
• metals can mostly be cleaned from their oxides also in arbitrary stoves with hydrogen gas.
• these conventional cleaning methods lead to sintering of the fine powders.
• the microwave plasma furnace even finest metal powders can be cleaned completely from their oxides within few minutes and without any changes of the particle size. Temperature control is made by use of a sufficiently short pulsed plasma. The power of the microwave furnace is always adjusted to the oxide properties and the grain size of the 5 metal.
• amorphous boron can be released from oxygen and the obtained product is an oxygen- free boron or boron with reduced oxygen content whereas boron is still amorphous.
• all materials, which contain oxygen impurities, can be purified by means of the process of the invention.
• materials are used as starting materials which have > 1 wt.-%, in particular ⁇ 4 wt.-% and preferably ⁇ 10 wt.-% of oxygen based on the total weight of the material.
• the oxygen impurity can be present as oxygen in a distributed form or also o in a bonded form, especially in the form of oxides.
• the process of the invention it is possible to considerably reduce the amount of oxygen, especially to a content of ⁇ 0.5 wt.%, more preferably to a content of ⁇ 0.1 wt.%, preferably ⁇ 0.05 wt.%, and even more preferably ⁇ 5 0.01 wt.-% of oxygen based on the total weight of the material.
• the actual content of oxygen which is achieved depends on the respective treatment conditions and can be adjusted by a skilled artisan depending on the desired final value.
• the treatment of the starting material is effected by a hydrogen-based plasma.
• a plasma advantageously contains ⁇ 5 mass%, in particular ⁇ 20 mass%, preferably ⁇ 50 mass%, in particular ⁇ 90 mass%, preferably ⁇ 99 mass% and more preferably ⁇ 99.5 mass% of hydrogen, however, can also completely consist of hydrogen.
• a gas atmosphere containing hydrogen and, if necessary, one or more inert gases having a desired pressure is provided.
• the pressure is advantageously 0.1 to 100, especially 1 to 20 bar.
• a pure hydrogen-based plasma or a plasma based on a mixture of hydrogen and at least one inert gas is selected from argon and nitrogen.
• the oxygen content in the plasma is preferably ⁇ 10 ppm, especially ⁇ 5 ppm, more preferably ⁇ 1 ppm and most preferably ⁇ 0,6 ppm.
• the oxygen content in the plasma is adjusted to 0.1 to 0.5 ppm.
• the water content in the plasma advantageously is ⁇ 10 ppm, especially ⁇ 5 ppm, more preferably ⁇ 1 ppm and more preferably ⁇ 0,1 ppm.
• the treatment with the hydrogen-based plasma can be carried out depending on the desired degree of removal of the oxygen for a variable duration, usually the duration between 0.5 to 10 h, especially between 2 and 5 h and often between 3 and 3.5 h are favourable.
• the plasma treatment is preferably performed at a temperature from 700 0 C to 1 ,500 0 C, in particular from 800°C to 1 ,100°C.
• the hydrogen plasma used according to the invention is a microwave induced plasma.
• a microwave radiation source an energy source having 100 to 2,000 W, especially 500 to 1,000 W at 1 to 10 Ghz, especially 2 to 3 Ghz can for example be used.
• H radicals and H + ions, generated in a plasma, in particular in a microwave induced plasma are very active so that in principal any kind of material can be purified by performing the inventive procedure.
• the H radicals und H + ions are active enough to remove oxygen from amorphous boron which purification was not possible with methods of the state of the art so far by retaining the amorphous structure.
• oxygen is removed in the presence of an oxygen getter.
• an oxygen getter greatly enhances the purification efficiency. While any oxygen getter material can be used espcecially good results have been achieved with titanium.
• the method according to the invention allows to perform a purification from oxygen impurities without contaminating the material by any other agent. In particular no reduction agents which might remain in the material are needed. Further, no microstructure changes occur which means that the structure of the raw material is the same as the microstructure of the treated material. This allows for example to maintain amorphous boron and just remove oxygen impurities without transforming the amorphous microstructure into a crystalline microstructure.
• the present invention is further elucidated by the following example.
• amorphous boron 99,999% with respect of metals, 4.05 ⁇ 0.21 mass.% of oxygen by ICP analysis
• a quartz ampoule together with an additional crucible, containing an oxygen getter (e.g. titanium). All described operations were performed in an argon-filled glove box with controlled atmosphere ( ⁇ 0.1 ppm H 2 O, 0.1 - 0.6 ppm O 2 ).
• the ampoule was evacuated, filled by the desired gas to the definite pressure and then sealed. Filling gas composition was varied to find the best one for the purification. Pure argon and nitrogen plasma treatment do not change the oxygen content. AiVH 2 based plasma (5% vol. of H 2 ) let to a reduction of oxygen content. The best results were achieved using pure hydrogen as the filling gas.
• the ampoules were opened and then the probes for the chemical analysis were prepared in the glove box.
• the best result (0.09 ⁇ 0.05 mass.% of oxygen after treatment) was achieved using H 2 plasma, Ti as a getter and a reaction time of about 3 to
• Powder X-ray diffraction investigation revealed, that both starting material and plasma-treated product did not show sharp diffraction peaks and revealed only a wide intensity bump at a lower diffraction angles. This confirms the amorphous state of the material. Scanning electron microscopial observation revealed, that in the plasma-treated products the starting particles are sintered to larger conglomerates.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Analytical Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Environmental & Geological Engineering (AREA)
• Biomedical Technology (AREA)
• Inorganic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Physical Or Chemical Processes And Apparatus (AREA)
• Gas Separation By Absorption (AREA)
• Solid-Sorbent Or Filter-Aiding Compositions (AREA)
• Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
• Manufacture And Refinement Of Metals (AREA)
• Drying Of Semiconductors (AREA)
• Catalysts (AREA)

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• 2006
  • 2006-05-17 JP JP2008511631A patent/JP4914438B2/ja not_active Expired - Fee Related
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  • 2006-05-17 US US11/914,593 patent/US7611686B2/en not_active Expired - Fee Related
  • 2006-05-17 RU RU2007146762/05A patent/RU2403953C2/ru not_active IP Right Cessation
  • 2006-05-17 EP EP06753692A patent/EP1893320B8/de not_active Not-in-force
  • 2006-05-17 CN CN2006800260708A patent/CN101222968B/zh not_active Expired - Fee Related
  • 2006-05-17 WO PCT/EP2006/004692 patent/WO2006122794A2/en not_active Ceased
  • 2006-05-17 DE DE602006011007T patent/DE602006011007D1/de active Active

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